Bis(pyridinium salts) useful as gelatin hardeners

ABSTRACT

CERTAIN BIS(PYRIDINUM SLATS) ARE USEFUL FOR HARDENING GELATIN, SUCH AS PHOTOGRAPHIC GELATIN. ADIPOLYBIS (NOXYMETHYLPYRIDINUM PERCHLORATE), ADIPOLYBIS(N-OXYMETHYL - 4 - PICOLINIUM PRCHLORATE), ADIPOLYBIS(N - ALPHA-OXYETHYLPYRIDINIUM PERCHLORATE) AND SEBACOYLBIS(N-OXYMETHYLPYRIDINIUM PERCHLORATE) ARE ILLUSTRATIVE OF THE NOVEL HARDENER COMPOUNDS.

United States Patent C) No n'awin Original application May 22, 1964,Ser. No. 369,629, now Patent No. 3,396,127, dated Aug. 6, 1968. Dividedand this application Feb. 2, 1968, Ser.

Int. Cl. C07d 31/34 US. Cl. 260-295 6 Claims ABSTRACT OF THE DISCLOSURECertain bis(pyridinium salts) are useful for hardening gelatin, such asphotographic gelatin. Adipolybis (N- oxymethylpyridinium perchlorate),adipolybis(N-oxymethyl 4 picolinium perchlorate), adipolybis(Nalpha-oxyethylpyridinium perchlorate) andsebacoylbis(N-oxymethylpyridinium perchlorate) are illustrative of thenovel hardener compounds.

This application is a division of our copending applicaiton Ser. No.369,629, filed May 22, 1964, now US Pat. 3,396,127 issued Aug. 6, 1968.

This invention relates to certain compounds found useful as photographichardeners and to gelatin compositions containing those hardeners.

Some compounds which have been suggested as hardeners for photographicemulsions or other gelatin solutions have been insufficiently effectivefor that purpose.

One object of our invention is to provide hardeners for photographicgelatin. Another object of our invention is to provide gelatincompositions useful photographically. A further object of our inventionis to provide certain compounds which are useful in the preparation ofphotographic products. Other objects of our invention will appearherein.

We have found that certain quaternary nitrogen type compounds, whichcompounds are free of deleterious photographic effects, are useful forhardening photographic emulsions or gelatin compositions generally. Wehave found that bis(alphacarbonyloxyalkyl quaternary nitrogen) salts andpolymeric analogs thereof are useful for hardening purposes inphotographic compositions. These hardeners are not only useful ingelatin compositions but also have been found to be effective forhardening polymers containing hydroxyl groups generally whenincorporated in compositions thereof prior to coating out onto asupport. We have found that several of the compounds in accordance without invention, in addition to having a hardening effect ongelatin-silver halide photographic emulsions, also exert a sensitizingeffect thereon.

The compounds of our invention are conveniently prepared by thealkylation of the appropriate tertiary amine with an appropriatebis(alpha-chloroalkyl carboxylate). In lieu thereof these compounds maybe prepared by the direct condensation of acid halide, aldehyde andtertiary amine by the procedure described by Iakubovics et al., J. Gen.Chem. U.S.S.R. Engl. Transl. 28, 1971 (1958). Compounds which have beenfound to be useful for hardening gelatin or some other polymericmaterial hav- 3,576,813 Patented Apr. 27, 1971 ing carboxyl groupstherein have the following general structural formula:

in which X is an acid anion such as halide, perchlorate or othersuitable acid anion; R is hydrogen or a lower alkyl radical such as of1-4 carbon atoms and B+ is a quaternary nitrogen residue from one of thefollowing bases: (1) pyridine or simple derivatives thereof as forexample picolines, 2-benzylpyridine, 2-(4-pyridyl) ethanol and the like,(2) a compound with a tertiary nitrogen in a bridgehead position as forexample quinuclidine, (3) an aliphatic or cyclic tertiary base as forexample trimethylamine, triethylamine, N-methylpiperidine and the like.Z represents a linking structure which may be either a valence bond, asaturated or unsaturated carbon chain or a heterogeneous chain composedpredominantly of carbon. It may be a cyclocarbon such as cyclohexyleneor phenylene, a chain including phenylene, cyclohexylene, or some otherradical or a chain having simple alkyl substituents thereon such asmethyl, ethyl, propyl, butyl and the like. The linking structure is mostconveniently (CH where n equals 110.

Where a bifunctional amine is used in preparing the hardener, forexample, N,N'-dimethylpiperazine, or where the nitrogen residue isderived from 1,4-diazabicyclo[2. 2.2[octane polymeric salts will beformed having good hardening activity. The following recurring structurerepresents polymers of this nature which are useful as hardeners inaccordance with our invention:

In this structure Z and X represent substituents as listed above and nrepresents the degree of polymerization,

' being a number from 2 to 20 or even more. R and R are hydrogen orlower alkyl or together they may form the hydrocarbon portion of a ring.

In using the hardeners in accordance with our invention they may beemployed in gelatin compositions either where gelatin is the mainsubstituent or in compositions in which gelatin is a carrier forsuspended material such as in gelatin-silver halide photographicemulsions, gelatinbarium sulfate compositions or other cases where somepigment or insoluble material is in suspension in the gelatin. Usefulcompositions are also prepared by incorporating these hardeners intosolutions or emulsions of polymers containing carboxyl groups as forexample acrylic acid copolymers. These hardeners are conveniently usedin proportions of 0.55%, based on the weight of the gelatin or otherpolymer to be hardened. However, it is to be understood that theinvention is not limited to these proportions as effective amountsoutside of this range may occasionally be employed.

The following examples illustrate the preparation of hardeners useful inaccordance with our invention.

Example l.-Adipoylbis (N-oxymethylpyridinium perchlorate) 4.86 grams ofbis(chlormethyl) adipate were dissolved in 25 ml. of dry pyridine andthe solution was heated on a steam bath for 2 hours. The precipitate wasisolated and converted to the perchlorate by a double decompositionreaction with sodium perchlorate. Recrystallization from water gavecolorless crystals, M.P. 206-207 (corn).

Example 2.Adipoylbis(N-oxymethyl-4-picolinium perchlorate) This compoundwas prepared in the same manner as described in Example 1 except that'y-picoline was substituted for the pyridine. The melting point of thecrystals obtained was 123425 (corn).

Example 3.Adipoylbis(N-alpha-oxyethylpyridinium perchlorate) The methoddescribed in Example 1 was followed except that an equivalent amount ofbis(alpha-chloroethyl)adipate was substituted for the bis(chlormethyl)adipate. The material obtained had no definite melting point and tendedto oil out on recrystallization.

Example 4.Sebacoylbis (N-oxymethylpyridinium perchlorate) This materialwas prepared by the procedure of Example 1 but using an equivalentamount of bis(chloromethyl) sebacate therein. The material obtained hada melting point of 168-171 (corn).

Example .Adipoylbis( l-oxymethyl-4-azal-azoniabicyclo [2.2.2] octanechloride) A solution was prepared of 4.86 grams ofbis(chlormethyl)adipate and 11.2 grams of l,4-diazabicyclo[2.2.2] octanein 25 ml. of acetonitrile. This solution was stirred at 25 C. Denseprecipitation and an exothermic reaction set in after 35 minutes. Theprecipitate was collected the next day and recrystallized fromalcohol-acetone. The product obtained had a melting point of l25l26.5(corn).

Example 6.Poly(1,4 diazoniabicyclo[2.2.2]0ctane-1,4- dimethyl adipatedichloride) A solution of equimolar quantities of the reagents ofExample 5 in acetonitrile was heated on the steam bath for one hour. Thematerial was purified by repeated dissolution in water and precipitationinto acetone.

The salts obtained in the above examples had the following structuralformula:

Samples of the compounds prepared by the above examples were added toseparate portions of a high-speed silver bromoiodide emulsion which hadbeen panchromatically sensitized with a cyanine dye. Each emulsionsample was coated on a cellulose acetate film support at a coverage of432 mg. of silver and 980 mg. of gelatin per square foot. A sample ofeach film coating was exposed on an Eastman 1B sensitometer, processedfor five minutes in Kodak DK-SO developer, fixed, washed and dried withthe following results:

TABLE II Percent Hardener of Cone, Rel. vertical g./100 swell Example g.of gel speed Gamma Fog in water 1 Control 100 1. 24 0. 10 609 1 89 1. 1809 349 5 87 1. 15 09 214-281 10 87 1. 07 08 102-256 2 Control 100 1. 1312 850 1 118 1. 17 14 570 3 107 1. I0 13 360 3 Control 100 1.30 16 750 197 1. 33 15 700 3 102 1. 27 15 530 6 102 l. 13 17 490 4 Control 100 1.27 17 990 3 1.05 20 370 6 53 93 29 230 5 Control 1. 23 13 860 1 107 1.30 14 640 3 89 1. l5 13 260 6 Control 100 1. 37 13 731 3 91 1. 13 11 2786 74 1. 07 11 10 71 97 .10 148 Example7.Adipoylbis(oxymethyltrimethylammonium perchlorate) A solution wasprepared by dissolving 7.29 grams of bis(chloromethyl)adipate and 45grams of trimethylamine in 25 ml. of acetonitrile. The solution wasstirred for 8 hours under reflux (using a Dry-Ice condenser) followingwhich it was allowed to stand over night at room temperature. The thickslurry which resulted was diluted with ether and the solids werecollected. The chloride obtained was dried and then converted to theperchlorate by a double decomposition reaction with sodium perchlorate.The product obtained was recrystallized from water, giving colorlesscrystals of the above mentioned compounds, M.P. 235236 C.

Example -8.-Adipolybis(oxyrnethyltriethylammonium perchlorate) Asolution as prepared of 30 ml. of triethylamine (dried over calciumhydride) and 4.86 grams of bis(chloromethyl) adipate in 25 ml. ofacetonitrile. The solution was stirred for 2 days for anhydrousconditions. The solids which precipitated (triethylamine hydrochloride)were filtered off and discarded. The filtrate was concentrated to removevolatiles and the residual oil obtained was converted to the perchlorateby a double decomposition reaction. Evaporation gave a saturated aqueoussolution of the perchlorate which yielded seed crystals by means ofwhich the Whole could be recrystallized froml methanol with seeding.Colorless crystals of the above mentioned compound were obtained, M.P.139-141 C.

Samples of the compounds prepared in Examples 7 and 8 were added toseparate portions of a high-speed silver bromoiodide emulsion which hadbeen panchromatically sensitized with a cyanine dye. Each emulsionsample was coated on cellulose acetate film support at a coverage of 459mg. of silver and 1040 mg. of gelatin per square foot. A sample of eachfilm coating and control samples were exposed on an Eastman 1Bsensitometer, processed for 5 minutes in Kodak DK-SO developer, fixed,washed, and dried with the following results:

Percent C0nc., vertical Hardener of g./l00 Rel. swell Example g of gelspeed Gamma Fog in water 7 Control 100 1.10 .11 810 100 1. 13 410 8Control 100 1. 25 12 810 106 1. 28 12 460 Examples 9, 10 and 11Hardening amounts of hardeners in accordance with the invention wereadded to gelatin containing coating composition as indicated below. Eachof the compositions was coated on cellulose acetate film support at therate of 750 mg. (dry weight) of composition per square footand dried aswas also a sample of composition without hardener. The swell in water ofeach coating was determined with the following results:

Percent Hardener Percent hardener Percent hardener 1n compo- SwellExample example in gelatin sition 1 in water Control 500 7 5 150 1 20 5150 5 20 5 120 1 Layer consisted of the designated percent hardener in acomposition %)5'75 gelatin and 75% ethyl acrylate-acrylic acid copolymer(sodium The invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof, but itwill be understood that variations that modifications can be effectedwithin the spirit and scope of the invention as described hereinabove,and as defined in the appended claims.

We claim:

1. A compound having the formula:

wherein X is an inorganic nonmetallic halo anion, each R is the samesubstituent selected from the group consisting of hydrogen and an alkylgroup having 1 to 4 carbon atoms, each B is the same member selectedfrom the group consisting of a pyridinium group and a picolinium groupand wherein said members are joined through their nitrogen atom to thecarbon atom of the UNITED STATES PATENTS 2,023,075 12/1935 Harris 2602952,089,602 8/ 1937 Granacher 260295 2,402,526 6/ 1946 Pikl 260 -2953,241,972 3/1966 Wilson 96111 3,312,711 4/1967 Koch 260295 3.144,45 6 8/1964 Motfett 260268 3,213,098 10/ 1965 Miller 260268 3,345,177 10/1967Wilson 260297 3,369,076 2/ 1968 Kaniecki 260567.'6 3,396,127 8/1968Burness et a1 2608 3,406,005 10/1968 Whitfield 260268UX DONALD G. DAVIS,Primary Examiner US. Cl. X.R.

gggg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,516 ,81'3 Dated April 21, 1971 Inventor) Donald M. Burness and Burton D.Wilson It is certified that error appears in the above-identified patentand that said Letters Potent are hereby corrected as shown below:

Column 6, line 3H, "3,213,098 should read 3 3: 9

Column 6, line 36, "3, 369,076" should read 3:3 9s

Signed and sealed this 18th day of April 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

